Abstract
One version of the tert -amino effect operating in tert- anilines possessing an ortho- vinyl substituent affords a fused tetrahydropyridine ring by an isomerization process with the formation of a new carbon-carbon bond between the vinyl and tert -amino moieties. Since its discovery in 1984, this type of cyclization has been efficiently used for the construction of fused-ring systems. However, it has been found that the electron-deficient heterocyclic analogues of tert -anilines, such as diazines, may undergo isomerization at considerably lower reaction rates and, as a consequence, their reactions may require harsh conditions. Recent synthetic studies have indicated that the rate and yield may be improved by incorporating the β-vinylic carbon atom into an electron-deficient ring and/or buttressing the tert -amino group, and/or performing the reaction by means of microwave irradiation.
This review describes relatively recent synthetic transformations involving this type of tert -amino effect and devotes special attention to structure-reactivity relationships including regio- and stereochemical aspects.
1 Introduction
2 The tert -Amino Effect: Type 2 Reactions
2.1 Substrates with a Dicyanovinyl Group
2.1.1 Benzene Derivatives
2.1.2 Pyridine Derivatives
2.1.3 Pyrimidine Derivatives
2.1.4 Pyridazine Derivatives
2.2 Substrates with a Cyclic Vinyl Substituent
2.2.1 Pyridazine Derivatives
2.2.2 Pyrimidine Derivatives
2.2.3 Benzene Derivatives
2.3 Microwave-Assisted Synthesis
2.4 Regio- and Stereochemical Features
3 Conclusions
Key words
tert -amino effect - ring closure - isomerization - substituent effects - spiro compounds - heterocycles - microwave-assisted synthesis
References
1 Pinnow J.
Ber. Dtsch. Chem. Ges.
1895,
28:
3039
2a Meth-Cohn O.
Suschitzky H.
Adv. Heterocycl. Chem.
1972,
14:
211
2b Meth-Cohn O.
Adv. Heterocycl. Chem.
1996,
65:
1
3 Quintela JM.
Recent Res. Dev. Org. Chem.
2003,
7:
259
4a Verboom W.
Reinhoudt DN.
Visser R.
Harkema S.
J. Org. Chem.
1984,
49:
269
4b Verboom W.
Reinhoudt DN.
Recl. Trav. Chim. Pays-Bas
1990,
109:
311
4c Verboom W.
Verboom C.
Eissink IM.
Lammerink BHM.
Reinhoudt DN.
Recl. Trav. Chim. Pays-Bas
1990,
109:
481
5a Nijhuis WHN.
Verboom W.
Abu El-Fadl A.
van Hummel GJ.
Reinhoudt DN.
J. Org. Chem.
1989,
54:
209
5b Kelderman E.
Noorlander-Bunt HG.
van Eeerden J.
Verboom W.
Reinhoudt DN.
Recl. Trav. Chim. Pays-Bas
1991,
110:
115
5c Tverdokhlebov AV.
Gorulya AP.
Tolmachev AA.
Kostyuk AN.
Chernega AN.
Rusanov EB.
Synthesis
2005,
13:
2161
6 Groenen LC.
Verboom W.
Nijhuis WHN.
Reinhoudt DN.
Van Hummel GJ.
Feil D.
Tetrahedron
1988,
44:
4637
7 Mátyus, P.; Bálint-Polonka, Á. unpublished results.
8a Ojea V.
Peinador C.
Vilar J.
Quintela JM.
Synthesis
1993,
152
8b Ojea V.
Muinelo I.
Figueroa MC.
Ruiz M.
Quintela JM.
Synlett
1995,
622
9a Wamhoff H.
Kramer-Hoß V.
Liebigs Ann./Recl.
1997,
1619
9b Bhuyan PJ.
Lekhok KC.
Sadhu JS.
J. Chem. Res., Synop.
1998,
502
10 Ojea V.
Muinelo I.
Quintela JM.
Tetrahedron
1998,
54:
927
11 Mátyus P.
Fuji K.
Tanaka K.
Heterocycles
1994,
37:
171
12 Schwartz A.
Beke Gy.
Kovári Z.
Böcskey Z.
Farkas Ö.
Mátyus P.
J. Mol. Struct.: Theochem.
2000,
528:
49
13 Mátyus P.
Maes BUW.
Riedl Zs.
Hajós G.
Lemière GyLF.
Tapolcsányi P.
Monsieurs K.
Éliás O.
Dommisse RA.
Krajsovszky G.
Synlett
2004,
1123
14 Halász-Dajka, B.; Mátyus, P. unpublished results.
15 Orlek BS.
Sammes PG.
Weller DJ.
J. Chem. Soc., Chem. Commun.
1993,
1412
16 Éliás O.
Károlyházy L.
Horváth Gy.
Harmat V.
Mátyus P.
J. Mol. Struct.: Theochem.
2003,
666-667:
625
17 Barbachyn MR, Dobrowolski PJ, Hurd AR, McNamara DJ, Palmer JR, Romero AG, Ruble JC, Sherry DA, Thomasco LM, and Toogood PL. inventors; Int. Pat. Appl. WO 2004/031195.
; Chem. Abstr. 2004 , 140 , 339202
18 Károlyházy L.
Regdon G.
Éliás O.
Beke Gy.
Tábi T.
Hódi K.
Erős I.
Mátyus P.
J. Mol. Struct.: Theochem.
2003,
666-667:
667
19 Kaval N.
Dehaen W.
Mátyus P.
Van der Eyken E.
Green Chem.
2004,
6:
125
20 Kaval N.
Halász-Dajka B.
Thanh GV.
Dehaen W.
Van der Eyken J.
Mátyus P.
Loupy A.
Van der Eyken E.
Tetrahedron
2005,
61:
9052
21 Nijhuis WHN.
Verboom W.
Abu El-Fadl A.
Harkema S.
Reinhoudt DN.
J. Org. Chem.
1989,
54:
199
22 Nijhuis WHN.
Verboom W.
Reinhoudt DN.
J. Am. Chem. Soc.
1987,
109:
3136
23 Ojea V.
Quintela JM.
Heterocycles
1993,
36:
1337
24 Mátyus, P.; Éliás, O. manuscript in preparation.
25a Ogawa K.
Harada J.
Endo M.
Takeuchi Y.
Tetrahedron Lett.
1997,
38:
5663
25b Oosterbaan WD.
Havenith RWA.
van Walree CA.
Jenneskens LW.
Gleiter R.
Kooijman H.
Spek AL.
J. Chem. Soc., Perkin Trans. 2
2001,
1066
26 Bondi A.
J. Phys. Chem.
1964,
68:
441
27 Sugimura T.
Kohno H.
Nagano S.
Nishida F.
Tai A.
Chem. Lett.
1999,
1143
28 Beke Gy.
Gergely A.
Szász Gy.
Szentesi A.
Nyitray J.
Barabás O.
Harmath V.
Mátyus P.
Chirality
2002,
14:
365
